Coordination precipitation polymerization process for olefin polymerization and polyolefins

Abstract

The application relates to the technical field of polyolefins, and discloses a coordination precipitation polymerization method for olefin polymerization and a polyolefin, the method comprising mixing olefin monomers, a catalyst and an additive, and performing a polymerization reaction; the olefin monomers contain nonpolar monomers and polar monomers; the nonpolar monomers are selected from one or more than two of ethylene, alpha-olefins and internal olefins; the polar monomers are selected from one or more than two of enol, unsaturated carboxylic acids and unsaturated carboxylic acid esters; and the catalyst is selected from a single-metallocene pre-transition metal complex shown in formula (I). The application can eliminate the catalyst loading process, realize olefin homogeneous catalyst polymerization self-forming, and prepare polyolefins with good particle morphology.

Description

Technical Field

[0001] This invention relates to the field of polyolefin technology, and more specifically to a coordination precipitation polymerization method for olefin polymerization and a polyolefin. Background Technology

[0002] Polyolefin products are inexpensive, have excellent performance, and are widely used. Olefin polymerization catalysts and polymerization processes are the core of polyolefin technology. From the development of olefin polymerization catalysts, there are two main aspects: (1) developing polyolefin resin catalysts that can prepare special or superior performance, such as metallocene catalysts and non-metallocene transition metal catalysts; (2) on the basis of further improving catalyst performance, simplifying catalyst preparation processes, reducing catalyst costs, and developing environmentally friendly technologies to improve efficiency and enhance competitiveness. Before the 1980s, the focus of polyethylene catalyst research was on pursuing catalyst efficiency. After nearly 30 years of effort, the catalytic efficiency of polyethylene catalysts has increased by orders of magnitude, thereby simplifying the production process of polyolefins and reducing energy and material consumption. Ziegler-Natta catalysts have been around for nearly 60 years. During this period, although polyolefin catalysts such as metallocene and non-metallocene have emerged, there are still many problems in their industrialization, such as the high cost of co-catalysts and the difficulty in loading the main catalyst. In recent years, olefin polymerization catalyst products have emerged in large numbers at home and abroad, and the stability and polymerization catalytic activity of catalysts have also been continuously improved. However, there are still shortcomings in terms of hydrogen sensitivity adjustment, control of catalyst particle regularity and particle size distribution. Current research is still focused on developing spherical or near-spherical supported catalysts with simple processes, good hydrogen sensitivity adjustment, and uniform particle size distribution.

[0003] Commonly used polymerization processes in the polyolefin industry include slurry polymerization, gas-phase polymerization, and bulk polymerization, with most catalysts being supported catalysts. Monomers are inserted into and grow in a complex form on the supported catalyst to prepare particulate polymer particles. The stability of the catalyst in the plant and the morphology of the polymer largely depend on the particle morphology, particle strength, and particle size distribution of the catalyst. Therefore, catalyst support technology has a crucial effect on the olefin polymerization process.

[0004] In his book *Principles of Polymerization*, Odian points out that precipitation polymerization is a polymerization process that begins in a homogeneous system but can rapidly transform into a heterogeneous system. Typically, precipitation polymerization occurs in solutions of monomers or monomers and solvents, and the resulting polymer precipitates out because it is insoluble in the reaction medium. In recent years, precipitation polymerization has attracted widespread research interest because it can produce surface-pure polymer microspheres. However, precipitation polymerization is mostly applied to free radical polymerization reactions. If precipitation polymerization and co-coordination polymerization can be combined, and the polymerization process can be controlled in commonly used solvents for coordination polymerization, it is possible to directly prepare polymer particles with good particle morphology from unloaded transition metal complexes via precipitation polymerization, which has promising application prospects. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of complex catalyst loading processes and polymer deashing and granulation post-processing in existing technologies, and to provide a coordination precipitation polymerization method for olefin polymerization and polyolefins. This method controls the polymerization reaction process to achieve the direct preparation of polyolefins with good particle morphology by precipitation polymerization under the action of monocyclic pre-transition metal complexes. This eliminates the complicated catalyst loading process, greatly simplifies the preparation process of the main catalyst, has low equipment requirements, low energy consumption, and low environmental pollution.

[0006] To achieve the above objectives, the present invention provides a coordination precipitation polymerization method for olefin polymerization, comprising mixing an olefin monomer, a catalyst, and an auxiliary agent, and carrying out a polymerization reaction; wherein the olefin monomer contains a nonpolar monomer and a polar monomer; the nonpolar monomer is selected from one or more of ethylene, α-olefins, and internal olefins; the polar monomer is selected from one or more of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters; and the catalyst is selected from a monocyclic pretransition metal complex of formula (I).

[0007]

[0008] Wherein, M is selected from Group IVB metals; Ar is selected from substituted or unsubstituted C6-C20 aryl groups; X is selected from halogens and C1-C10 hydrocarbon groups, and n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl groups; R1 is OR 21 R 22 , where R 21 and R 22 Each is independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 R 22 It connects with O to form a ring or ring system, where m is 0 or 1.

[0009] Preferably, the structural formula of the monoclonal pre-transition metal complex is shown in formula (II).

[0010]

[0011] Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon groups.

[0012] Preferably, the monoclonal pre-transition metal complex is selected from the following complexes:

[0013] Complex 1: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0014] Complex 2: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0015] Complex 3: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0016] Complex 4: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0017] Complex 5: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0018] Complex 6: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0019] Complex 7: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0020] Complex 8: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0021] Complex 9: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0022] Complex 10: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0023] Complex 11: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0024] Complex 12: The complex shown in formula (II), wherein M is Ti, L1 = 1-methyl-2,4-cyclopentadienyl, R 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0025] Complex 13: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0026] Complex 14: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0027] Complex 15: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0028] Complex 16: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0029] Complex 17: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R15 H is H, X is methyl, n = 2, m = 0;

[0030] Complex 18: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0031] Complex 19: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0032] Complex 20: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0033] Complex 21: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0034] Complex 22: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0035] Complex 23: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0036] Complex 24: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0037] Complex 25: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0038] Complex 26: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0039] Complex 27: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0040] Complex 28: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0041] Complex 29: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n = 2, m = 0;

[0042] Complex 30: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0043] Complex 31: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0044] Complex 32: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0045] Complex 33: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0046] Complex 34: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0047] Complex 35: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0048] Complex 36: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0049] Complex 37: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0050] Complex 38: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0051] Complex 39: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0052] Complex 40: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0053] Complex 41: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0054] Complex 42: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0055] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0056] Complex 44: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0057] Complex 45: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0058] Complex 46: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0059] Complex 47: The complex shown in formula (II), wherein M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0060] Complex 48: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0061] Complex 49: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0062] Complex 50: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0063] Complex 51: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0064] Complex 52: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0065] Complex 53: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0066] Complex 54: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0067] Complex 55: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0068] Complex 56: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0069] Complex 57: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0070] Complex 58: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0071] Complex 59: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0072] Complex 60: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0073] Complex 61: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0074] Complex 62: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0075] Complex 63: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0076] Complex 64: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=1, R1 is tetrahydrofuran, m=1;

[0077] Complex 65: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R...11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0078] Complex 66: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0079] Complex 67: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0080] Complex 68: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0081] Complex 69: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0082] Complex 70: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0083] Complex 71: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0084] Complex 72: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0085] Complex 73: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 R1 is methoxy, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0086] Complex 74: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0087] Complex 75: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0088] Complex 76: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0089] Complex 77: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0090] Complex 78: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0091] Complex 79: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0092] Complex 80: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0093] Complex 81: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0094] Complex 82: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is Cl, n = 2, R1 is 2-methyltetrahydrofuran, m = 1;

[0095] Complex 83: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0096] Complex 84: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0097] Complex 85: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0098] Complex 86: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0099] Complex 87: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0100] Complex 88: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0101] Complex 89: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0102] Complex 90: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0103] Complex 91: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0104] Complex 92: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0105] Complex 93: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0106] Complex 94: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0107] Complex 95: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0108] Complex 96: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0109] Complex 97: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R...11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0110] Complex 98: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0111] Complex 99: The complex shown in formula (II), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0112] Complex 100: The complex shown in formula (II), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0113] Complex 101: The complex shown in formula (II), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0114] Complex 102: The complex shown in formula (II), wherein M is Hf, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0115] Complex 103: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0116] Complex 104: The complex shown in formula (II), wherein M is Hf, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0117] Complex 105: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0118] Complex 106: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n = 2, m = 0;

[0119] Complex 107: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0120] Complex 108: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0121] Complex 109: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0122] Complex 110: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0123] Complex 111: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0124] Complex 112: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0125] Complex 113: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0126] Complex 114: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0127] Complex 115: The complex shown in formula (II), wherein M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0128] Complex 116: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0129] Complex 117: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0130] Complex 118: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0.

[0131] Preferably, the enol is selected from monomers represented by formula (G1).

[0132]

[0133] L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

[0134] Preferably, the unsaturated carboxylic acid is selected from monomers represented by formula (G2).

[0135]

[0136] L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

[0137] Preferably, the unsaturated carboxylic acid ester is selected from monomers represented by formula (G3).

[0138]

[0139] Among them, L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, L4 is selected from C1-C30 alkylene groups with side groups, and L6 is selected from C1-C30 alkyl groups.

[0140] Preferably, the additive is selected from one or more of organoaluminum compounds, organoboron compounds, and organosilicon compounds.

[0141] Preferably, the organoaluminum compound is AlY. n X 1 3-n Wherein, Y is selected from H, C1-C20 saturated or unsaturated hydrocarbon groups, and C1-C20 saturated or unsaturated alkyloxy groups, preferably C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl, or C6-C20 aryl; X 1 Selected from halogens, preferably chlorine or bromine; 0 <n≤3。

[0142] Preferably, the organoboron compound is an aromatic boron and / or a borate.

[0143] Preferably, the aromatic boron is selected from substituted or unsubstituted phenyl boron, and more preferably tris(pentafluorophenyl)boron.

[0144] Preferably, the borate is selected from N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate and / or triphenylmethyl tetra(pentafluorophenyl)borate.

[0145] Preferably, the organosilicon compound is an alkylsilane compound.

[0146] Preferably, the alkylsilicon compound has the general formula SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl groups, and H2, H3 and H4 are each independently selected from C1-C10 alkyl groups or halogens.

[0147] Preferably, when the additive contains an organoaluminum compound, the molar ratio of the amount of aluminum in the organoaluminum compound to the amount of M in the catalyst is (10-10000000):1.

[0148] Preferably, when the auxiliary contains an organoboron compound, the molar ratio of the amount of boron in the organoboron compound to the amount of M in the catalyst is (0.1-1000):1;

[0149] Preferably, when the additive contains an organosilicon compound, the molar ratio of the amount of silicon in the organosilicon compound to the amount of M in the catalyst is (10-10000000):1.

[0150] Preferably, when the additive is a combination of organoaluminum compound, organoboron compound and organosilicon compound, the molar ratio of the total amount of aluminum, boron and silicon in the additive to the amount of M in the catalyst is (10-11000000):1.

[0151] Preferably, the polymerization reaction is carried out in the presence of a solvent.

[0152] Preferably, the solvent is selected from one or more of alkanes, haloalkanes, and aromatic hydrocarbons.

[0153] Preferably, the alkane is selected from one or more of C3-C20 alkanes.

[0154] Preferably, the general formula of the haloalkane is R 1 X 2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogens, m2+n2≥1, R 1 Selected from C1-C10 alkyl or alkenyl groups, R 2 Selected from C1-C10 alkylene or alkenylene groups.

[0155] Preferably, the aromatic hydrocarbon has the general formula R 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl, and C1-C10 alkanes.

[0156] Preferably, the conditions for the polymerization reaction include: a temperature of -50 to 180°C and a time of 10 to 200 minutes.

[0157] A second aspect of the present invention provides a polyolefin prepared by the coordination precipitation polymerization method for olefin polymerization described above, wherein the polyolefin is spherical or near-spherical in shape.

[0158] Preferably, the average particle size of the polyolefin is 0.02-50 mm.

[0159] Preferably, the weight-average molecular weight of the polyolefin is 10,000-800,000.

[0160] Preferably, the molecular weight distribution index of the polyolefin is ≤10.

[0161] Preferably, the polyolefin has a melting point of 90-140°C.

[0162] Compared with the prior art, the present invention has the following beneficial effects:

[0163] (1) The coordination precipitation polymerization method for olefin polymerization described in this invention is a homogeneous reaction solution before the olefin monomers polymerize. The monocyclic transition metal complex does not need to be loaded on an inorganic or organic support. By controlling the polymerization process, the polyolefin precipitates out of the system and the polyolefin self-forms to prepare spherical or near-spherical polyolefins. Therefore, this invention can eliminate the catalyst loading process and realize the self-forming of olefin homogeneous catalyst polymerization to prepare olefin polymers with good particle morphology.

[0164] (2) The coordination precipitation polymerization method for olefin polymerization described in this invention can prepare spherical or near-spherical polar polyolefins with polar groups and high melting points, thereby introducing polar groups into the polyolefin chain, improving the interfacial compatibility of the polyolefin, and retaining its crystallinity.

[0165] (3) The coordination precipitation polymerization method for olefin polymerization described in this invention does not require subsequent processing such as granulation, and can directly obtain spherical or near-spherical polyolefins, which greatly simplifies the preparation process of the main catalyst, has low equipment requirements, low energy consumption, and low environmental pollution. Therefore, this invention has good industrial application prospects.

[0166] (4) The coordination precipitation polymerization method for olefin polymerization described in this invention directly prepares well-shaped spherical or near-spherical polyolefins by selecting the pre-transition metal complex of the monoclonal monomer, the olefin monomer and suitable reaction conditions. The obtained polyolefins are not prone to scaling in the reactor and are easy to transport.

[0167] (5) The coordination precipitation polymerization method for olefin polymerization described in this invention can catalyze the polymerization reaction of olefin monomers with high activity, which can greatly simplify the process and reduce production costs. Detailed Implementation

[0168] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0169] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0170] This invention provides a coordination precipitation polymerization method for olefin polymerization, comprising mixing an olefin monomer, a catalyst, and an accelerant, and carrying out a polymerization reaction; wherein the olefin monomer contains a nonpolar monomer and a polar monomer; the nonpolar monomer is selected from one or more of ethylene, α-olefins, and internal olefins; the polar monomer is selected from one or more of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters; and the catalyst is selected from a monocyclic pretransition metal complex of formula (I).

[0171]

[0172] Wherein, M is selected from Group IVB metals; Ar is selected from substituted or unsubstituted C6-C20 aryl groups; X is selected from halogens and C1-C10 hydrocarbon groups, and n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl groups; R1 is OR 21 R 22 , where R 21 and R 22 Each is independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 R 22 It connects with O to form a ring or ring system, where m is 0 or 1.

[0173] In a preferred embodiment, the structural formula of the monoclonal pre-transition metal complex is shown in formula (II).

[0174]

[0175] Among them, R 11 -R 15Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon groups. In a preferred embodiment, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0176] In formulas (I) and (II), M is selected from group IVB metals. In preferred cases, M is selected from titanium, zirconium, and hafnium.

[0177] In formulas (I) and (II), X is selected from halogens and C1-C10 hydrocarbon groups. In preferred cases, X is selected from halogens and C1-C8 hydrocarbon groups (such as C1-C6 alkyl groups).

[0178] In formulas (I) and (II), n is 1 or 2, indicating that the number of X groups attached to metal M is n. In the preferred case, n is 1.

[0179] In formulas (I) and (II), L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, and substituted or unsubstituted fluorenyl. Preferably, the L1 group is selected from cyclopentadienyl, methyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,4-trimethyl-cyclopentadienyl, 1,2,3,4-tetramethyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, tert-butyl-cyclopentadienyl, isobutyl-cyclopentadienyl, indenyl, butyl-indenyl, 1-methyl-indenyl, 2-methyl-indenyl, 1-phenyl-indenyl, trihydro-indenyl, and fluorenyl.

[0180] In equations (I) and (II), R1 is OR 21 R 22 , where R 21 and R 22 Each is independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 R 22 It connects with O to form a ring or ring system. In a preferred case, R 21 and R 22 Each is independently selected from substituted or unsubstituted C1-C6 hydrocarbon groups, and R 21 R 22 It can be interconnected with O to form a five-membered or six-membered ring. In a further preferred embodiment, R1 is tetrahydrofuran (C4H8O), 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,2-dimethyltetrahydrofuran, etc.

[0181] In formulas (I) and (II), m can be 0 or 1. When m is 0, it indicates that the R1 group does not exist.

[0182] In this invention, "substituted or unsubstituted" means containing a substituent, which can be selected from halogens, hydroxyl groups, C1-C6 alkyl groups, halogenated C1-C6 alkyl groups, C1-C6 alkoxy groups and halogenated C1-C6 alkoxy groups.

[0183] In this invention, the alkyl group (such as C1-C6 alkyl or C1-C10 alkyl) may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0184] In this invention, the alkoxy group (such as C1-C6 alkoxy) may be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0185] In this invention, the aryl group (such as C6-C8 aryl, C6-C15 aryl, or C6-C20 aryl) may be selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0186] In this invention, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0187] In a preferred embodiment, the monocyclic pretransition metal complex is selected from the following complexes: Complex 1: the complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0188] Complex 2: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0189] Complex 3: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0190] Complex 4: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0191] Complex 5: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R15 H is H, X is Cl, n = 2, m = 0;

[0192] Complex 6: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0193] Complex 7: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0194] Complex 8: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0195] Complex 9: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0196] Complex 10: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0197] Complex 11: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0198] Complex 12: The complex shown in formula (II), wherein M is Ti, L1 = 1-methyl-2,4-cyclopentadienyl, R 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0199] Complex 13: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0200] Complex 14: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0201] Complex 15: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0202] Complex 16: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0203] Complex 17: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0204] Complex 18: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n = 2, m = 0;

[0205] Complex 19: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0206] Complex 20: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0207] Complex 21: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0208] Complex 22: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0209] Complex 23: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0210] Complex 24: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0211] Complex 25: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0212] Complex 26: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0213] Complex 27: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n = 2, m = 0;

[0214] Complex 28: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0215] Complex 29: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n = 2, m = 0;

[0216] Complex 30: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0217] Complex 31: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R 11 R 13 and R 15 For H, R 12 and R 14X is a methyl group, n = 2, m = 0;

[0218] Complex 32: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0219] Complex 33: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0220] Complex 34: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0221] Complex 35: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0222] Complex 36: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0223] Complex 37: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0224] Complex 38: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0225] Complex 39: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0226] Complex 40: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0227] Complex 41: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0228] Complex 42: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran (-OC4H8), m = 1;

[0229] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0230] Complex 44: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0231] Complex 45: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0232] Complex 46: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0233] Complex 47: The complex shown in formula (II), wherein M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0234] Complex 48: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0235] Complex 49: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0236] Complex 50: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0237] Complex 51: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0238] Complex 52: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0239] Complex 53: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0240] Complex 54: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R...11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0241] Complex 55: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0242] Complex 56: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0243] Complex 57: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0244] Complex 58: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0245] Complex 59: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0246] Complex 60: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0247] Complex 61: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0248] Complex 62: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0249] Complex 63: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0250] Complex 64: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=1, R1 is tetrahydrofuran, m=1;

[0251] Complex 65: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0252] Complex 66: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0253] Complex 67: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0254] Complex 68: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0255] Complex 69: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0256] Complex 70: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0257] Complex 71: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0258] Complex 72: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0259] Complex 73: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 R1 is methoxy, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0260] Complex 74: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0261] Complex 75: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0262] Complex 76: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0263] Complex 77: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0264] Complex 78: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0265] Complex 79: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0266] Complex 80: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0267] Complex 81: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0268] Complex 82: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13The methyl group is methoxy, X is Cl, n = 2, R1 is 2-methyltetrahydrofuran, m = 1;

[0269] Complex 83: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0270] Complex 84: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0271] Complex 85: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0272] Complex 86: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0273] Complex 87: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0274] Complex 88: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0275] Complex 89: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0276] Complex 90: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0277] Complex 91: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0278] Complex 92: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0279] Complex 93: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The methyl group is X, the Cl group is n=2, and the tetrahydrofuran group is m=1.

[0280] Complex 94: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, where X is methyl, n = 2, and R1 is tetrahydrofuran, m = 1;

[0281] Complex 95: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R...11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is -CH2C6H5, n = 2, R1 is tetrahydrofuran, m = 1;

[0282] Complex 96: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The methoxy group is X, which is Cl, n = 2, and R1 is tetrahydrofuran, m = 1.

[0283] Complex 97: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0284] Complex 98: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0285] Complex 99: The complex shown in formula (II), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0286] Complex 100: The complex shown in formula (II), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0287] Complex 101: The complex shown in formula (II), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0288] Complex 102: The complex shown in formula (II), wherein M is Hf, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0289] Complex 103: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R 11 -R 15H is H, X is Cl, n = 2, m = 0;

[0290] Complex 104: The complex shown in formula (II), wherein M is Hf, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0291] Complex 105: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0292] Complex 106: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n = 2, m = 0;

[0293] Complex 107: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0294] Complex 108: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0295] Complex 109: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0296] Complex 110: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0297] Complex 111: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0298] Complex 112: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0299] Complex 113: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0300] Complex 114: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0;

[0301] Complex 115: The complex shown in formula (II), wherein M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n = 2, m = 0;

[0302] Complex 116: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n = 2, m = 0;

[0303] Complex 117: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n = 2, m = 0;

[0304] Complex 118: The complex shown in formula (II), wherein M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n = 2, m = 0.

[0305] In this invention, the method for preparing the above-mentioned monoclonal pre-transition metal complex includes the following steps:

[0306] (1) The compound shown in formula (III) is reacted with the compound shown in formula (IV) to obtain the ligand shown in formula (V);

[0307] (2) The ligand is reacted with a dehydrogenating agent and then reacted with an M metal compound, wherein the metal M in the M metal compound is selected from group IVB metals and the M metal compound contains at least one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indene, tetrahydroindene and substituted or unsubstituted fluorenyl.

[0308]

[0309] The definition of Ar is the same as described above.

[0310] In a preferred embodiment, the reaction process of step (1) is as shown in the following reaction formula.

[0311]

[0312] Among them, R 11 -R 15 The definition is the same as described above.

[0313] In the method described in this invention, the compound represented by formula (III) can be of type S and / or type R.

[0314] In the method described in this invention, preferably, the transition metal M in the M metal compound is selected from titanium, zirconium, and hafnium. More preferably, the M metal compound is selected from cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, methyl-cyclopentadienyl titanium trichloride, n-butyl-cyclopentadienyl titanium trichloride, tert-butyl-cyclopentadienyl titanium trichloride, indene titanium trichloride, fluorenyl titanium trichloride, butyl-indene-titanium trichloride, 1-methyl-indene titanium trichloride, 2-methyl-indene titanium trichloride, 1-phenyl-indene-titanium trichloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, methyl-cyclopentadienyl zirconium trichloride, 1,3-dimethyl-cyclopentadienyl zirconium trichloride, 1,2,4-trimethyl-cyclopentadienyl zirconium trichloride, n-butyl-cyclopentadienyl zirconium trichloride, tert-butyl-cyclopentadienyl zirconium trichloride, etc. Zirconium chloride, indene-zirconium trichloride, fluorenyl-zirconium trichloride, butyl-indene-zirconium trichloride, 1-methyl-indene-zirconium trichloride, 2-methyl-indene-zirconium trichloride, 1-phenyl-indene-zirconium trichloride, cyclopentadienyl-1,2-dimethoxy-ethyl-zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, methyl-cyclopentadienyl hafnium trichloride Hafnium chloride, 1,2,3,4-tetramethyl-cyclopentadienyl-hafnium chloride, n-butyl-cyclopentadienyl-hafnium chloride, tert-butyl-cyclopentadienyl-hafnium chloride, isobutyl-cyclopentadienyl-hafnium chloride, indene-hafnium chloride, fluorenyl-hafnium chloride, trihydro-indene-hafnium chloride, and cyclopentadienyl-1,2-dimethoxy-ethyl-hafnium chloride.

[0315] In the method described in this invention, preferably, in the reaction process of step (1), the compound shown in formula (III) is first reacted with the dehydrogenating agent, and then reacted with the compound shown in formula (IV).

[0316] In steps (1) and (2), the dehydrogenating agents used may be the same or different, and each is independently selected from at least one of NaH, KH, n-butyllithium and methyllithium.

[0317] In one specific embodiment, the preparation process of step (1) includes: dissolving the compound shown in formula (III) in anhydrous diethyl ether under a protective gas atmosphere (such as nitrogen), adding a dehydrogenating agent (such as n-butyllithium) at room temperature, stirring at room temperature, adding tetrahydrofuran, and further stirring the resulting black solution containing precipitate; then adding the compound shown in formula (VI), stirring at room temperature, and adding NH4Cl aqueous solution for quenching; then extracting the organic phase with ethyl acetate, drying the obtained organic phase with anhydrous sodium sulfate, recrystallizing with dichloromethane / hexane to obtain a yellow crystalline compound; then adding methanol and concentrated hydrochloric acid, refluxing the reaction, removing the organic solvent after the reaction is complete, dissolving the product in ethyl acetate, adding NaHCO3 aqueous solution for neutralization, extracting the organic phase, and then sequentially drying, filtering, concentrating, and column chromatography to obtain the ligand shown in formula (VII).

[0318] In one specific embodiment, the preparation process of step (2) includes: dissolving the ligand obtained in step (1) in tetrahydrofuran in a protective gas atmosphere (such as nitrogen), adding an excess of dehydrogenating agent (such as NaH, KH, etc.), stirring at room temperature, filtering to remove the dehydrogenating agent, then adding a tetrahydrofuran solution of the M metal compound, reacting overnight at room temperature, drying the solvent, adding dichloromethane to dissolve, filtering to remove the filter cake, concentrating the filtrate, adding heptane to recrystallize, and obtaining the monoclonal pretransition metal complex of the present invention.

[0319] In this invention, the α-olefin is selected from one or more of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0320] In this invention, the internal olefin refers to an olefin whose double bond is not at the terminal position. An internal olefin of an olefin can be a mixture of multiple isomers or a single internal olefin. For example, butene can be 1-C4, cis-2-C4, trans-2-C4, and isobutene, or a mixture of one or more isomers. The catalyst structure and the composition of the mixed olefins have a certain influence on the structure and properties of the polymer product.

[0321] In this invention, the enol is selected from the monomers represented by formula (G1).

[0322]

[0323] L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

[0324] In a preferred embodiment, in formula (G1), L5 and L2 are H; L3 is H, a C1-C10 alkyl group, or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group with a side group, preferably a C1-C10 alkylene group with a side group, more preferably a C1-C6 alkylene group with a side group. The number of carbons in the C1-C30 alkylene group with a side group refers to the number of carbons on the straight chain, excluding the number of carbons on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group with a side group (methyl).

[0325] In this invention, in formula (G1), the side group is selected from one or more of halogens, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C1-C20 alkyl groups, hydroxylated C1-C20 alkyl groups, and alkoxy-substituted C1-C20 alkyl groups.

[0326] In a preferred embodiment, in formula (G1), the side group is selected from halogens, phenyl groups, and substituted or unsubstituted C1-C6 alkyl groups.

[0327] More preferably, in formula (G1), the substituted or unsubstituted C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, or hexyl.

[0328] In this invention, the enol is selected from at least one of the following compounds: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1,1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2,4-dimethyl-4-penten-2-ol, 4-enyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-butenol. En-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2,3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2,5-dimethyl -1-Hepten-4-ol, 2,6-Dimethyl-7-octen-2-ol, 2-Hydroxy-2,4,5-Trimethyl-6-Heptene, 2-Methyl-3-hydroxy-7-octene, 3-Methyl-3-hydroxy-6-heptene, 2-Methyl-2-hydroxy-7-octene, 3-Methyl-3-hydroxy-7-octene, 4-Methyl-2-hydroxy-7-octene, 4-Methyl-3-hydroxy-7-octene, 5-Methyl-3-hydroxy-7-octene, 6-Methyl-3-hydroxy-7-octene, 3-Ethyl-3-hydroxy-7-octene, 1,2-Dihydroxy-7-octene, 2,6-Dimethyl-2,6 -Dihydroxy-7-octene, 2,6-dimethyl-2,3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, 2-methyl-2-hydroxy-3,5-dichloro-7-octene, 3,4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3,5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2,3-diol, 2,6-dimethyl-7-octen-2,6-diol.

[0329] In this invention, the unsaturated carboxylic acid is selected from the monomers represented by formula (G2).

[0330]

[0331] L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

[0332] In a preferred embodiment, in formula (G2), L5 and L2 are H; L3 is H, a C1-C10 alkyl group, or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group with a side group, preferably a C1-C10 alkylene group with a side group, more preferably a C1-C6 alkylene group with a side group. The number of carbons in the C1-C30 alkylene group with a side group refers to the number of carbons on the straight chain, excluding the number of carbons on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group with a side group (methyl).

[0333] In this invention, in formula (G2), the side group is selected from one or more of halogens, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C1-C20 alkyl groups, hydroxylated C1-C20 alkyl groups, and alkoxy-substituted C1-C20 alkyl groups.

[0334] In a preferred embodiment, in formula (G2), the side group is selected from halogens, phenyl groups, and substituted or unsubstituted C1-C6 alkyl groups.

[0335] More preferably, in formula (G2), the substituted or unsubstituted C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, or hexyl.

[0336] In this invention, the unsaturated carboxylic acid is selected from at least one of the following compounds: 2-methyl-4-pentenoic acid, 2,3-dimethyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2,2,3-trimethyl-4-pentenoic acid, 2,3,3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2-(2-methylpropyl)-4-pentenoic acid, 2,2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,2,3,3-tetramethyl-4-pentenoic acid, 2-methyl-5-hexenoic acid, 2- Ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2,3-dimethyl-5-hexenoic acid, 2,2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2-(1-methylpropyl)-5-hexenoic acid, 2,2,3-trimethyl-5-hexenoic acid, 2,2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2,3-dimethyl-6-heptenoic acid, 2,4-dimethyl-6-heptenoic acid, 2,2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2 -Isopropyl-6-heptenic acid, 2,3,4-trimethyl-6-heptenic acid, 2-methyl-2-ethyl-6-heptenic acid, 2-(1-methylpropyl)-6-heptenic acid, 2,2,3-trimethyl-6-heptenic acid, 2,2-diethyl-6-heptenic acid, 2-methyl-7-octenic acid, 2-ethyl-7-octenic acid, 2-propyl-7-octenic acid, 2,3-dimethyl-7-octenic acid, 2,4-dimethyl-7-octenic acid, 2,2-dimethyl-7-octenic acid, 2-isopropyl-5-methyl-7-octenic acid, 2-isopropyl-7-octenic acid, 2,3,4-trimethyl-7-octenic acid, 2-methyl- 2-Ethyl-7-octenic acid, 2-(1-methylpropyl)-7-octenic acid, 2,2,3-trimethyl-7-octenic acid, 2,2-diethyl-7-octenic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2,3-dimethyl-8-nonenoic acid, 2,4-dimethyl-8-nonenoic acid, 2,2-dimethyl-8-nonenoic acid, 2,2-diethyl-8-nonenoic acid, 2-isopropyl-5-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2,3-dimethyl-9-decenoic acid, 2,4-dimethyl-9-decenoic acid, 2-methyl-10-undecenoic acid.

[0337] In this invention, the unsaturated carboxylic acid ester is selected from the monomers shown in formula (G3).

[0338]

[0339] Wherein, L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, L4 is selected from C1-C30 alkylene groups having side groups, and L6 is selected from C1-C30 alkyl groups. In a preferred embodiment, L6 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, and even more preferably a C1-C6 alkyl group.

[0340] In a preferred embodiment, in formula (G3), L5 and L2 are H; L3 is H, a C1-C10 alkyl group, or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group with a side group, preferably a C1-C10 alkylene group with a side group, more preferably a C1-C6 alkylene group with a side group. The number of carbons in the C1-C30 alkylene group with a side group refers to the number of carbons on the straight chain, excluding the number of carbons on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group with a side group (methyl).

[0341] In this invention, in formula (G3), the side group is selected from one or more of halogens, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C1-C20 alkyl groups, hydroxylated C1-C20 alkyl groups, and alkoxylated C1-C20 alkyl groups.

[0342] In a preferred embodiment, in formula (G3), the side group is selected from halogens, phenyl groups, and substituted or unsubstituted C1-C6 alkyl groups.

[0343] More preferably, in formula (G3), the substituted or unsubstituted C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, or hexyl.

[0344] In this invention, the unsaturated carboxylic acid ester is selected from at least one of the following compounds: methyl 2-methyl-3-butenoate, methyl 2-methyl-4-pentenoate, ethyl 2-methyl-4-pentenoate, methyl 2,3-dimethyl-4-pentenoate, ethyl 2-methyl-3-butenoate, methyl 2,3-dimethylbutenoate, methyl 2-ethyl-3-butenoate, methyl 2,2-dimethyl-3-butenoate, methyl 2-methyl-3-methylenepentenoate, ethyl 2,3-dimethyl-3-butenoate, methyl 2-vinylhexanoate, ethyl 2-ethyl-3-butenoate, methyl 2-vinyl-3-pentanoate, methyl 2-vinyl-4-methyl-4-pentanoate, methyl 2,2-dimethyl-3-butene. Ethyl acetate, methyl 2-hydroxy-2-methyl-3-butenoate, isobutyl 2-methyl-3-butenoate, ethyl 2-(1-methylethyl)-3-butenoate, methyl 2,2,3-trimethyl-3-butenoate, ethyl 2-vinylhexanoate, methyl 2-ethyl-2-methyl-3-butenoate, methyl 3-methyl-5-hexenoate, methyl 4-methyl-5-hexenoate, ethyl 4-methyl-5-hexenoate, methyl 2-methyl-6-heptenoate, methyl 2,4-dimethyl-5-hexenoate, methyl 2-ethyl-5-hexenoate, methyl 3-methyl-5-hexenoate, methyl 4-methyl-5-hexenoate, methyl 2-ethyl-4-pentenoate, methyl 2-propyl-4-pentenoate, 2 2-propyl-5-hexenoate methyl ester, 2-propyl-4-pentenoate methyl ester, 2-butyl-5-hexenoate methyl ester, 3-vinylhexanoate methyl ester, 2-(2-propen-1-yl)-4-pentanoate methyl ester, 2-(3-buten-1-yl)-5-hexenoate methyl ester, 3,3-dimethyl-5-hexenoate methyl ester, 3-propyl-5-hexenoate ethyl ester, 3,3-dimethyl-5-hexenoate ethyl ester, 3,4,4-trimethyl-5-hexenoate methyl ester, 3-(1,1-dimethylethyl)-5-hexenoate ethyl ester, 3-methyl-2-oxo-5-hexenoate ethyl ester, 2-vinyl-3,3-dimethyl-5-hexanoate methyl ester, methyl-β-vinylbenzopropionate, 3-methyl-5-hexenoate Benzyl ester, methyl 2-propyl-6-heptenoate, methyl 2-methyl-6-heptenoate, ethyl 2-methyl-6-heptenoate, methyl 2,2-dimethyl-6-heptenoate, ethyl 2,4-dimethyl-6-heptenoate, ethyl 2-propyl-6-heptenoate, ethyl 2,2-dimethyl-6-heptenoate, 1,3-dimethyl 2-(4-penten-1-yl)malonic acid, 2-methyl-1,1-dimethyl 6-heptenoate, tert-butyl 2-methyl-3-butenoate, ethyl 2-isopropyl-3-butenoate, methyl 2-isobutyl-4-pentenoate, methyl 2,2-dimethyl-4-pentenoate, methyl 3,3-dimethyl-4-pentenoate, ethyl 3,3-dimethyl-4-pentenoate, 2,2-Dimethyl-4-pentenoate ethyl ester, 2-n-propyl-4-pentenoate methyl ester, 2-isopropyl-4-pentenoate methyl ester, 2-methyl-4-pentenoate isobutyl ester, allyl malonate diethyl ester, allyl malonate dimethyl ester, allyl succinic anhydride, 2-methyl-4-pentenoate ethyl ester, 2-methyl-4-pentenoate methyl ester, 3-methyl-4-pentenoate methyl ester, 3-ethyl-4-pentenoate methyl ester, 3-methyl-4-pentenoate isobutyl ester, 2-(tert-) Ethyl butyl (-4-pentenoate), 3-allyl dihydrofuran-2(3H)-one, methyl 2-(dimethylamino)-2-methylpent-4-enoate, methyl 3-methyl-4-pentenoate, methyl 2-methyl-5-hexenoate, methyl 2,2-dimethyl-5-hexenoate, ethyl 2,2-dimethyl-5-hexenoate, benzyl 2-methyl-5-hexenoate, methyl 4,4-dimethyl-6-heptenoate, methyl 2,4-dimethyl-9-decenoate.

[0345] In this invention, the additive is selected from one or more of organoaluminum compounds, organoboron compounds, and organosilicon compounds.

[0346] In this invention, when the additive contains an organoaluminum compound, the organoaluminum compound is AlY. n X 1 3-n (alkylaluminum or alkylaluminum halide); wherein Y is selected from H, C1-C20 saturated or unsaturated hydrocarbon groups and C1-C20 saturated or unsaturated alkyloxy groups, preferably C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl; X 1 Selected from halogens, preferably chlorine or bromine; 0 <n≤3。

[0347] In this invention, C1-C20 alkyl groups can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, or 4-n-butylcyclohexyl; C1-C20 alkoxy groups can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, or tert-pentoxy; C7-C20 aralkyl groups can be phenylmethyl, phenylethyl, phenyln-propyl, phenylisopropyl, phenyln-butyl, or phenyl tert-butyl; C6-C20 aryl groups can be phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, or vinylphenyl.

[0348] In a preferred embodiment, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum (AliBu3), tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, dichloroethylaluminum, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO).

[0349] In a further preferred embodiment, the organoaluminum compound is methylaluminoxane (MAO).

[0350] In this invention, when the adjuvant contains an organoboron compound, the organoboron compound is an aromatic boron and / or a borate.

[0351] In this invention, the aromatic boron is selected from substituted or unsubstituted phenyl boron, preferably tris(pentafluorophenyl)boron.

[0352] In this invention, the borate is selected from N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate and / or tetra(pentafluorophenyl)borate triphenylmethyl salt.

[0353] In this invention, when the additive contains an organosilicon compound, the organosilicon compound is an alkylsilane compound.

[0354] In this invention, the general formula of the alkylsilicon compound is SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl groups, and H2, H3 and H4 are each independently selected from C1-C10 alkyl groups or halogens.

[0355] In a preferred embodiment, the alkylsilane compound is selected from one or more of trimethylchlorosilane, dichlorodimethylsilane, propyl dimethylchlorosilane, dichloroethylmethylsilane, tert-butyldimethylchlorosilane, diisopropylchlorosilane, trichloroethylsilane, chloromethyldimethylchlorosilane, di-tert-butylchlorosilane, dichloro(methyl)propylsilane, methyltrichlorosilane, and trichloroethylsilane.

[0356] In this invention, when the additive contains an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to element M in the catalyst is (10-10,000,000):1, preferably (10-100,000):1, and more preferably (100-10,000):1. Specifically, the molar ratio of aluminum in the organoaluminum compound to element M in the catalyst can be 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, or 10000:1.

[0357] In this invention, when the auxiliary contains an organoboron compound, the molar ratio of boron in the organoboron compound to element M in the catalyst is (0.1-1000):1, preferably (0.1-500):1. Specifically, the molar ratio of boron in the organoboron compound to element M in the catalyst can be 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, or 500:1.

[0358] In this invention, when the additive contains an organosilicon compound, the molar ratio of silicon in the organosilicon compound to element M in the catalyst is (10-10,000,000):1, preferably (10-200,000):1. Specifically, the molar ratio of silicon in the organosilicon compound to element M in the catalyst can be 10:1, 20:1, 50:1, 100:1, 500:1, 1000:1, 1500:1, 2000:1, 5000:1, 10000:1, 100000:1, or 200000:1.

[0359] In this invention, when the additive is a combination of organoaluminum compounds, organoboron compounds, and organosilicon compounds, the molar ratio of the total amount of aluminum, boron, and silicon in the additive to the amount of element M in the catalyst is (10-1,1000,000):1, preferably (10-200,000):1. Specifically, the molar ratio of the total amount of aluminum, boron, and silicon in the additive to the amount of element M in the catalyst can be 10:1, 20:1, 50:1, 100:1, 500:1, 1000:1, 1500:1, 2000:1, 5000:1, 10000:1, or 200000:1.

[0360] In this invention, the polymerization reaction is carried out in the presence of a solvent in order to make the polymerization reaction more complete.

[0361] In a preferred embodiment, the solvent is selected from one or more of alkanes, haloalkanes, and aromatic hydrocarbons.

[0362] In this invention, the alkane is selected from one or more of C3-C20 alkanes, preferably one or more of C3-C10 alkanes, more preferably one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, and even more preferably one or more of hexane, heptane and cyclohexane.

[0363] In this invention, the general formula of the haloalkane is R. 1 X2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogens, m2+n2≥1, R 1 Selected from C1-C10 alkyl or alkenyl groups, R 2 Selected from C1-C10 alkylene or alkenylene groups. The alkenyl group refers to a straight-chain alkenyl, branched alkenyl, or cycloalkenyl group; specifically, the alkenyl group is vinyl, allyl, or butenyl.

[0364] In a preferred embodiment, the haloalkane is selected from one or more of chloroform, dichloromethane, dichloroethane, dichloropropane, and trichloroethylene.

[0365] In this invention, the general formula of the aromatic hydrocarbon is R. 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl, and C1-C10 alkanes, where Ph represents a benzene ring. In a preferred embodiment, the aromatic hydrocarbon is selected from one or more of pentylbenzene, ethylbenzene, xylene, toluene, and benzene.

[0366] In a preferred embodiment, the polymerization reaction is carried out under anhydrous and oxygen-free conditions.

[0367] In this invention, the nonpolar monomer with ≤3 carbon atoms is generally a gas, and its amount is adjusted by controlling the pressure of the reaction system. In some specific embodiments, the amount of the nonpolar monomer is such that the pressure of the reaction system is 1-20 atm, preferably 5-15 atm. Specifically, when the nonpolar monomer is ethylene, the ethylene pressure in the reaction system is 1-20 atm, preferably 5-15 atm, specifically, for example, 5 atm, 8 atm, 10 atm, 11 atm, 12 atm, 13 atm, 14 atm, or 15 atm.

[0368] In this invention, the pressure refers to absolute pressure.

[0369] In this invention, the polar monomer is generally a liquid, and its amount is adjusted by controlling the concentration of the polar monomer in the liquid raw material. In some specific embodiments, the concentration of the polar monomer in the liquid raw material (typically including the polar monomer, catalyst, auxiliaries, and solvent) is 0.01-6000 mmol / L, preferably 0.1-1000 mmol / L, more preferably 1-500 mmol / L, and even more preferably 30-500 mmol / L. Specifically, the concentration of the polar monomer in the polymerization raw material can be 30 mmol / L, 50 mmol / L, 100 mmol / L, 150 mmol / L, 200 mmol / L, 250 mmol / L, 300 mmol / L, 350 mmol / L, 400 mmol / L, 450 mmol / L, or 500 mmol / L.

[0370] In this invention, the concentration of the catalyst in the liquid feedstock is 0.00001-100 mmol / L, preferably 0.0001-1 mmol / L, more preferably 0.001-0.5 mmol / L, and even more preferably 0.002-0.1 mmol / L. Specifically, the concentration of the catalyst in the liquid feedstock can be 0.002 mmol / L, 0.004 mmol / L, 0.006 mmol / L, 0.008 mmol / L, 0.01 mmol / L, 0.02 mmol / L, 0.04 mmol / L, 0.06 mmol / L, 0.08 mmol / L, or 0.1 mmol / L.

[0371] In this invention, the conditions for the polymerization reaction include: a temperature of -50 to 180°C and a time of 10 to 200 minutes. Preferably, the temperature of the polymerization reaction is -20 to 100°C, more preferably 20 to 100°C. Specifically, the temperature of the polymerization reaction can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C; the time of the polymerization reaction is 20 to 60 minutes. Specifically, the time of the polymerization reaction can be 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes.

[0372] A second aspect of the present invention provides a polyolefin prepared by the coordination precipitation polymerization method for olefin polymerization described above, wherein the polyolefin is spherical or near-spherical in shape.

[0373] In this invention, the average particle size of the polyolefin is 0.02-50 mm, preferably 0.05-50 mm, and more preferably 0.2-20 mm. Specifically, the average particle size of the spherical or near-spherical polymer can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm, or 20 mm.

[0374] In this invention, the weight-average molecular weight of the polyolefin is 10,000-800,000, preferably 10,000-500,000. Specifically, the molecular weight of the polyolefin can be 10,000, 20,000, 30,000, 40,000 or 50,000.

[0375] In this invention, the molecular weight distribution index of the polyolefin is ≤10, preferably 1.5-10. Specifically, the molecular weight distribution index of the polyolefin can be 1.5, 2, 2.5, 3, 3.5, 4, 6, 8 or 10.

[0376] In this invention, the molecular weight distribution index represents M. w / M n .

[0377] In this invention, the melting point of the polyolefin is 90-140℃. Specifically, the melting point of the polyolefin can be 90℃, 100℃, 110℃, 120℃, 125℃, 130℃, 135℃ or 140℃.

[0378] In this invention, the density of the polyolefin is 0.3-0.85 g / cm³. 3 The preferred value is 0.4-0.75 g / cm³. 3 Specifically, the density of the spherical or near-spherical polymer can be 0.4 g / cm³. 3 0.45g / cm 3 0.5g / cm 3 0.55g / cm 3 0.6g / cm 3 0.65g / cm 3 0.7g / cm 3 0.75g / cm 3 .

[0379] In this invention, the density is measured using the method in GB / T6343-2009.

[0380] In this invention, according to the coordination precipitation polymerization method, nonpolar monomers and polar monomers undergo polymerization in the presence of an unsupported catalyst to prepare spherical or spherical polymer particles. This method not only eliminates the complicated catalyst loading process, but also greatly simplifies the polymer deashing and granulation post-processing steps, which can inject new vitality into olefin polymerization technology.

[0381] The following examples further illustrate the coordination precipitation polymerization method for olefin polymerization and the polyolefins described in this invention. These examples are implemented based on the technical solution of this invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of this invention is not limited to the following examples.

[0382] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0383] The polymer was washed with a dilute acid solution before measurement to ensure that the metal content in the polymer was ≤50ppm.

[0384] The analytical and characterization instruments used in this invention are as follows:

[0385] 1. Nuclear magnetic resonance spectrometer: Bruker DMX 300 (300MHz), tetramethylsilyl (TMS) as internal standard, used at 25℃ to test the structure of complex ligands.

[0386] 2. Comonomer content of the copolymer: using... 13 The analysis was performed using C NMR spectroscopy on a 400MHz Bruker Avance 400 NMR spectrometer, with a 10mm PASEX 13 probe, at 130°C by dissolving the polymer sample in deuterated tetrachloroethane.

[0387] 3. Polymer molecular weight and molecular weight distribution index (PDI) (PDI = M w / M n ): The standard was determined at 150℃ using a PL-GPC220 column with trichlorobenzene as the solvent (standard: PS, flow rate: 1.0 mL / min, column: 3×Plgel 10um M1×ED-B300×7.5nm).

[0388] 4. Activity measurement method: Gravimetric analysis. The calculation method for polymerization activity is: Polymerization activity = Polymerization activity / Polymerization activity.

[0389] Weight of material (g) / metal complex (mol) × 60 / polymerization time (min).

[0390] 5. Polymer density test method: Refer to GB / T 6343-2009 for testing.

[0391] Example 1

[0392] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0393] In a nitrogen atmosphere, the compound shown in formula (III) (11.23 g, 30 mmol, S type) was dissolved in anhydrous diethyl ether (150 mL), and a 2.7 M, 33.3 mL, 90 mmol solution of n-butyllithium was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h, and then tetrahydrofuran (150 mL) was added. The resulting black solution containing the precipitate was stirred for another 1 h. Diphenylphosphine chloride (PPh2Cl) (90 mmol, 16.7 mL) was added at 0 °C, and the mixture was stirred at room temperature for 1 h. Then, an aqueous solution of NH4Cl was added. Quenching with 5 mL of ethyl acetate; extracting the organic phase with ethyl acetate, drying the obtained organic phase with anhydrous sodium sulfate, recrystallizing with dichloromethane / hexane to give a yellow crystalline compound (15.54 g); adding methanol (100 mL) and 5 mL of concentrated hydrochloric acid, refluxing for 16 h, monitoring the reaction by TLC until completion, removing the organic solvent, dissolving the product in ethyl acetate, neutralizing with NaHCO3 aqueous solution, extracting the organic phase, drying with anhydrous MgSO4, filtering, concentrating, and column chromatography (dichloromethane as solvent) to give ligand I1 in 67% yield; 1 H NMR (400MHz, CDCl3): δ=5.41 (s, 2H), 7.13-7.15 (m, 2H), 7.24-7.29 (m, 4H), 7.38-7.45 (m, 22H), 7.62-7.64 (m, 2H); 31 P NMR (162MHz, CDCl3): δ = -17.19(s); High-resolution mass spectrometry: Theoretical value: 654.19; Measured value: 655.20;

[0394] In a nitrogen atmosphere, ligand I1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A tetrahydrofuran solution of pentamethylcyclopentadienyl zirconium trichloride (0.666 g, 2 mmol) was added dropwise (-78 °C), and the mixture was reacted overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to give a yellow complex 43 with a yield of 77%. 1¹H NMR (400 MHz, CDCl₃): δ = 2.00 (m, 30H), 3.63 (m, 8H), 1.97 (m, 8H), 6.63–7.56 (m, 22H), 7.58–7.80 (m, 6H), 7.95–8.10 (m, 2H); Elemental analysis showed C2... 72 H 76 Cl4O4P2Zr2: Theoretical calculated values: C, 62.14; H, 5.51; Tested values: C, 62.32; H, 5.62;

[0395] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500mL of heptane, 30mmol (6.0mL) of 2,6-dimethyl-7-octen-2-ol, 36mL of AliBu3 (1.0mol / L n-pentane solution), and 3.5mL of MAO (1.53mol / L toluene solution) were added to the reactor, along with 3.5mg (2.5μmol) of complex 43. The reaction was carried out at 30℃ with an ethylene pressure of 10atm and stirred for 30 minutes. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A1. The polymerization activity of polyolefin A1 was 6.73×10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A1 is 1.72 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A1 is 3.5, the molar content of hydroxyl groups in polyolefin A1 is 1.14%, the polymer melting point of polyolefin A1 is 121.4℃, the average particle size of spherical polymers in polyolefin A1 is 2.10 mm, and the density of polyolefin A1 is 0.573 g / cm³. 3 The yield of spherical polymers in polyolefin A1 was 66%.

[0396] Example 2

[0397] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0398] In this embodiment, the preparation method and process of complex 43 are the same as those of complex 43 in Example 1;

[0399] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), and 4.8mg (6.0μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the reactor, along with 3.5mg (2.5μmol) of complex 43. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 20 minutes. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A2. The polymerization activity of polyolefin A2 was 9.32 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A2 is 2.23 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A2 is 3.28, the molar content of carboxyl groups in polyolefin A2 is 1.22%, the melting point of polyolefin A2 is 127.3°C, the average particle size of spherical polymers in polyolefin A2 is 1.94 mm, and the density of polyolefin A2 is 0.732 g / cm³. 3 The yield of spherical polymers in polyolefin A2 was 67%.

[0400] Example 3

[0401] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0402] In this embodiment, the preparation method and process of complex 43 are the same as those of complex 43 in Example 1;

[0403] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h. While still hot, a vacuum was applied and the reactor was purged three times with N2 gas. 3.0 mL of pentane, 0.5 mL (3.1 mmol) of methyl 3,3-dimethyl-4-pentenoate, 1.10 mL of AliBu3 (3.0 mol / L hexane solution), and 0.4 mL of triphenylmethyl tetra(pentafluorophenyl)borate (3.0 mmol / L dichloromethane solution) were added to the reactor. 0.1 mL of complex 43 (3.0 mmol / L dichloromethane solution) was added. The reaction was carried out at 20 °C with an ethylene pressure of 10 atm and stirred for 20 min. Finally, the reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A3. The polymerization activity of polyolefin A3 was 2.32 × 10⁻⁶. 5 g·mol -1 ·h -1The weight-average molecular weight of polyolefin A3 is 1.12 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A3 is 3.37, the ester molar content in polyolefin A3 is 2.04%, the average particle size of the spherical polymers in polyolefin A3 is 0.42 mm, and the yield of spherical polymers in polyolefin A3 is 65%.

[0404] Example 4

[0405] Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0406] In this embodiment, the preparation method and process of complex 43 are the same as those of complex 43 in Example 1;

[0407] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h. While still hot, a vacuum was applied and the reactor was purged three times with N2 gas. 4.0 mL of heptane, 600 μL (3.86 mmol) of 2-octene, 100 μL of AliBu3 (0.1 mol / L heptane solution), and 60.0 μL of triphenylmethyl tetra(pentafluorophenyl)borate (1.0 mmol / L dichloromethane solution) were added to the reactor. 50 μL of complex 43 (1.0 mmol / L dichloromethane solution) was added. The reactor was stirred for 30 min at 60 °C while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A4. The polymerization activity of polyolefin A4 was 8.22 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A4 is 0.82 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A4 is 3.2, the melting point of polyolefin A4 is 119.7℃, the average particle size of the near-spherical polymer in polyolefin A4 is 0.57mm, and the yield of the spherical polymer in polyolefin A4 is 55%.

[0408] Example 5

[0409] Complex 2: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0410] In this embodiment, the preparation method and process of ligand I1 are the same as those of ligand I1 in Example 1;

[0411] In a nitrogen atmosphere, ligand I1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A tetrahydrofuran solution of pentamethylcyclopentadienyl titanium trichloride (0.578 g, 2 mmol) was added dropwise, and the mixture was reacted overnight at room temperature. The solvent was dried, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to give orange complex 2 with a yield of 79%. 1 ¹H NMR (300 MHz, CDCl₃): δ = 2.28 (s, 30H), 7.13–7.16 (m, 2H), 7.27–7.30 (m, 4H), 7.38–7.48 (m, 22H), 7.61–7.64 (m, 2H); Elemental analysis showed C 64 H 60 Cl4O2P2Ti2: Theoretical values: C, 66.23; H, 5.21; Test values: C, 66.41; H, 5.52;

[0412] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), and 4.8mg (6.0μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the reactor, along with 3.0mg (2.5μmol) of complex 2. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 minutes. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A5. The polymerization activity of polyolefin A5 was 2.12 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A5 is 1.63 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A5 is 3.32, the molar content of carboxyl groups in polyolefin A5 is 1.20%, the melting point of polyolefin A5 is 126.2℃, the average particle size of spherical polymers in polyolefin A5 is 1.34 mm, and the density of polyolefin A5 is 0.712 g / cm³. 3 The yield of spherical polymers was 62%.

[0413] Example 6

[0414] Complex 2: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0415] In this embodiment, the preparation method and process of complex 2 are the same as those of complex 2 in Example 5;

[0416] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h. While still hot, a vacuum was applied and the reactor was purged three times with N2 gas. 3.0 mL of pentane, 0.5 mL (3.1 mmol) of methyl 3,3-dimethyl-4-pentenoate, 1.1 mL of AliBu3 (in 3.0 mol / L hexane solution), and 0.5 mL of triphenylmethyl tetra(pentafluorophenyl)borate (in 3.0 mmol / L dichloromethane solution) were added to the polymerization system. 0.1 mL of complex 2 (in 3.0 mmol / L dichloromethane solution) was added. The reaction was carried out at 20 °C with an ethylene pressure of 10 atm and stirred for 10 min. Finally, the reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A6. The polymerization activity of polyolefin A6 was 0.92 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A6 is 0.77 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A6 is 3.22, the ester molar content in polyolefin A6 is 2.03%, the average particle size of the near-spherical polymer in polyolefin A6 is 0.41 mm, and the yield of spherical polymer in polyolefin A6 is 63%.

[0417] Example 7

[0418] Complex 98: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0419] In this embodiment, the preparation method and process of ligand I1 are the same as those of ligand I1 in Example 1;

[0420] In a nitrogen atmosphere, ligand I1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A tetrahydrofuran solution of pentamethylcyclopentadienyl hafnium trichloride (0.840 g, 2 mmol) was added dropwise (-78 °C), and the mixture was reacted overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to give a white complex 98 with a yield of 80%. 1¹H NMR (300 MHz, CDCl₃): δ = 1.93–2.06 (m, 30H), 7.05–7.07 (m, 2H), 7.17–7.21 (m, 4H), 7.28–7.37 (m, 22H), 7.53–7.55 (m, 2H); Elemental analysis showed C2 64 H 60 Cl4Hf2O2P2: Theoretical values: C, 54.06; H, 4.25; Test values: C, 54.27; H, 4.46;

[0421] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h. While still hot, a vacuum was applied and the reactor was purged three times with N2 gas. 4.0 mL of heptane, 600 μL of 2-octene, 100 μL of AliBu3 (0.1 mol / L heptane solution), and 60.0 μL of triphenylmethyl tetra(pentafluorophenyl)borate (1.0 mmol / L dichloromethane solution) were added to the polymerization system. 50 μL of complex 98 (1.0 mmol / L dichloromethane solution) was also added. The reaction was carried out at 60 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A7. The polymerization activity of polyolefin A7 was 5.17 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A7 is 10.82 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A7 is 3.1, the melting point of polyolefin A7 is 113.7℃, the average particle size of the near-spherical polymer in polyolefin A7 is 0.55mm, and the yield of the spherical polymer in polyolefin A7 is 58%.

[0422] Example 8

[0423] Complex 98: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n = 2, m = 0;

[0424] In this embodiment, the preparation method and process of complex 98 are the same as those of complex 98 in Example 7;

[0425] A 1L stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 2 hours. While still hot, a vacuum was applied and the reactor was purged three times with N2 gas. 400 mL of pentane, 14.3 mL (90 mmol) of methyl 3,3-dimethyl-4-pentenoate, 100 mL of AliBu3 (1.0 mol / L hexane solution), and 3.3 mL of MAO (1.53 mol / L) were then added to the polymerization system. 3.5 mg (2.5 μmol) of complex 98 was added. The reaction was maintained at 10 atm ethylene pressure at 25℃ and stirred for 10 minutes. Finally, the mixture was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution to obtain polyolefin A8. The polymerization activity of polyolefin A8 was 2.44 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight of polyolefin A8 is 9.31 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A8 is 3.21, the ester molar content in polyolefin A8 is 1.22%, the average particle size of the near-spherical polymers in polyolefin A8 is 3.20 mm, and the yield of spherical polymers is 69%.

[0426] Example 9

[0427] Complex 78: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The form is -CF3, X is Cl, n = 2, R1 is tetrahydrofuran, m = 1;

[0428] In a nitrogen atmosphere, the compound (3.74 g, 10 mmol, R type) of formula (III) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h. Tetrahydrofuran (120 mL) was added, and the resulting black solution containing the precipitate was stirred for another 1 h. Bis(3,5-bis(trifluoromethyl)phenyl)chlorophosphine (30 mmol, 14.78 g) was added at 0 °C. After stirring at room temperature for 1 h, NH4+ was added. The reaction was quenched with 5 mL of 4Cl aqueous solution, and the organic phase was extracted with ethyl acetate. The obtained organic phase was dried with anhydrous sodium sulfate and recrystallized from dichloromethane / hexane to give a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid were added, and the mixture was refluxed for 16 h. After the reaction was monitored by TLC, the organic solvent was removed, the product was dissolved in ethyl acetate, neutralized with NaHCO3 aqueous solution, and the organic phase was extracted. The product was dried with anhydrous MgSO4, filtered, concentrated, and subjected to column chromatography (using dichloromethane as solvent) to give ligand I2 in 40% yield. 1H NMR (400MHz, DMSO): δ=9.10 (s, 2H), 8.17 (s, 2H), 8.13 (s, 2H), 8.08 (dd, J=13.3, 6.5Hz, 8H), 7.81 (d, J=7.6Hz, 2H), 7.56 (d, J=8.4Hz, 2H), 7.27 (dd, 4H), 6.90 (d, J=8.2Hz, 2H); 31 P NMR (162MHz, DMSO): δ = -8.37 (s); 1 ¹H NMR (400MHz, CDCl₃): δ = 5.14 (s, 2H), 7.08–7.11 (m, 2H), 7.41–7.46 (m, 4H), 7.63 (d, 2H), 7.78–7.81 (m, 2H), 7.84 (d, 4H), 7.86 (d, 4H), 7.91 (s, 2H), 7.94 (s, 2H); High-resolution mass spectrometry: Theoretical value: 1198.09; Measured value: 1198.95;

[0429] Under a nitrogen atmosphere, ligand I2 (1.20, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A tetrahydrofuran solution of pentamethylcyclopentadienylzirconium trichloride (0.666 g, 2 mmol) was added dropwise, and the mixture was reacted overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated. Heptane was added for recrystallization to give a yellow complex 78 with a yield of 77%. Elemental analysis showed that C... 80 H 68 Cl4F 24 O4P2Zr2: Theoretical values: C, 49.64; H, 3.54; Test values: C, 49.84; H, 3.61;

[0430] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500 mL of pentane, 30 mmol (4.0 mL) of 3,3-dimethyl-4-pentenoic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 4.8 mg (2.5 μmol) of complex 78. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 minutes. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A9. The polymerization activity of polyolefin A9 was 8.72 × 10⁻⁶. 5 g·mol -1 ·h -1The weight-average molecular weight of polyolefin A9 is 1.93 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin A9 is 3.11, the molar content of carboxyl groups in polyolefin A9 is 1.16%, the melting point of polyolefin A9 is 126.2°C, the average particle size of spherical polymers in polyolefin A9 is 1.32 mm, and the density of polyolefin A9 is 0.672 g / cm³. 3 The yield of spherical polymers in polyolefin A9 is 60%.

[0431] Comparative Example 1

[0432] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500 mL of pentane, 30 mmol (4.0 mL) of 3,3-dimethyl-4-pentenoic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 3.6 mg (5.0 μmol) of complex F (synthesis reference: Dalton Trans., 2014, 43, 222-230). The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 20 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin D1. The polymerization activity of polyolefin D1 was 3.32 × 10⁻⁶. 5 g·mol -1 ·h -1 The molecular weight of polyolefin D1 is 0.82 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin D1 is 3.49, the molar content of carboxyl groups in polyolefin D1 is 1.14%, the average particle size of spherical polymers in polyolefin D1 is 1.42 mm, and the yield of spherical polymers in polyolefin D1 is 45%.

[0433]

[0434] Comparative Example 2

[0435] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 500 mL of pentane, 30 mmol (4.0 mL) of 3,3-dimethyl-4-pentenoic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.6 mg (5 μmol) of complex N (synthesis reference: JOURNAL OF POLYMER SCIENCE, PART A: POLYMERCHEMISTRY 2013, 51, 1585-1594). The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin D2. The polymerization activity of polyolefin D2 was 6.22 × 10⁻⁶. 4 g·mol -1 ·h -1 The molecular weight of polyolefin D2 is 0.53 × 10⁻⁶. 5 The molecular weight distribution index of polyolefin D2 is 4.12, the molar content of carboxyl groups in polyolefin D2 is 1.02%, and the density of polyolefin D2 is 0.792 g / cm³. 3 The yield of spherical polymers in polyolefin D2 is 30%.

[0436]

[0437] In this invention, compared with the complexes used in Comparative Examples 1 and 2, when the transition metal complex of this invention is used as the main catalyst, the resulting polyolefin has higher polymerization activity, the molecular weight of the resulting polyolefin is significantly higher than that of the polyolefins obtained in Comparative Examples 1 and 2, and the coordination precipitation polymerization method of this invention for olefin polymerization can prepare polar polyolefins with good particle morphology and polar groups.

[0438] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A coordination precipitation polymerization method for olefin polymerization, characterized in that, This method involves mixing olefin monomers, catalysts, and auxiliaries to carry out a polymerization reaction; The olefin monomer contains both nonpolar and polar monomers; The nonpolar monomer is selected from one or more of ethylene, α-olefins and internal olefins; The polar monomer is selected from one or more of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters; The catalyst is selected from the monoclonal pre-transition metal complex shown in formula (II). Formula (II) Wherein, M is selected from group IVB metals; R 11 -R 15 Each element is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon groups; X is selected from halogen, C1-C10 hydrocarbon groups, and n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl; R1 is OR 21 R 22 , where R 21 and R 22 Each is independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 R 22 It connects with O to form a ring or ring system, where m is 0 or 1.

2. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The monoclonal pre-transition metal complex is selected from the following complexes. Complex 1: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 2: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 3: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 4: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 5: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 6: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 7: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 8: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 9: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 10: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 11: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 12: The complex shown in formula (II), wherein M is Ti, L1 = 1-methyl-2,4-cyclopentadienyl, R 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 13: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 14: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 15: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 16: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 17: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 18: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, m=0; Complex 19: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 20: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 21: The complex shown in formula (II), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 22: The complex shown in formula (II), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 23: The complex shown in formula (II), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 24: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 25: The complex shown in formula (II), wherein M is Ti, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 26: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 27: The complex shown in formula (II), wherein M is Ti, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, m=0; Complex 28: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 29: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n=2, m=0; Complex 30: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 31: The complex shown in formula (II), wherein M is Ti, L1 is cyclopentadienyl, and R 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n=2, m=0; Complex 32: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 33: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 34: The complex shown in formula (II), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 35: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 36: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 37: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 38: The complex shown in formula (II), where M is Ti, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n=2, m=0; Complex 39: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 40: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 41: The complex shown in formula (II), where M is Ti, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 42: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 43: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 44: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 45: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 46: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 47: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 48: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 49: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 50: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 51: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 52: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 53: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 54: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 55: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 56: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 57: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 58: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 59: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 60: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 61: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 62: The complex shown in formula (II), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 63: The complex shown in formula (II), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 64: The complex shown in formula (II), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=1, R1 is tetrahydrofuran, m=1; Complex 65: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 66: The complex shown in formula (II), wherein M is Zr, L1 is tetrahydroindenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 67: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 68: The complex shown in formula (II), wherein M is Zr, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 69: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 70: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 13 R 14 and R 15 For H, R 12 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 71: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 72: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 73: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 R1 is methoxy, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 74: The complex shown in formula (II), wherein M is Zr, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 75: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 76: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 77: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The value is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 78: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 79: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 80: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 81: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The value is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 82: The complex shown in formula (II), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 is methoxy, X is Cl, n=2, R1 is 2-methyltetrahydrofuran, m=1; Complex 83: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 84: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 85: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The value is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 86: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 87: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 88: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 89: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The value is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 90: The complex shown in formula (II), where M is Zr, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 91: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 92: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is -CF3, n=2, R1 is tetrahydrofuran, m=1; Complex 93: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 is methyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 94: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 95: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The value is -CF3, X is -CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 96: The complex shown in formula (II), where M is Zr, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The methyl group is methoxy, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 97: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 98: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 99: The complex shown in formula (II), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 100: The complex shown in formula (II), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 101: The complex shown in formula (II), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 102: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 103: The complex shown in formula (II), where M is Hf, L1 is fluorene, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 104: The complex shown in formula (II), wherein M is Hf, L1 is phenyl-indenyl, and R... 11 -R 15 H is H, X is Cl, n=2, m=0; Complex 105: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 106: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R 11 R 13 R 14 and R 15 For H, R 12 The expression is -CF3, X is Cl, n=2, m=0; Complex 107: The complex shown in formula (II), wherein M is Hf, L1 is cyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 108: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 109: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 110: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 111: The complex shown in formula (II), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n=2, m=0; Complex 112: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 113: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 114: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0; Complex 115: The complex shown in formula (II), where M is Hf, L1 is indenyl, and R... 11 R 13 and R 15 For H, R 12 and R 14 X is a methyl group, n=2, m=0; Complex 116: The complex shown in formula (II), where M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 The expression is -CF3, X is Cl, n=2, m=0; Complex 117: The complex shown in formula (II), where M is Hf, L1 is fluorene, and R... 11 R 13 and R 15 For H, R 12 and R 14 The expression is -CF3, X is Cl, n=2, m=0; Complex 118: The complex shown in formula (II), where M is Hf, L1 is fluorene, and R... 11 R 12 R 14 and R 15 For H, R 13 It is a methoxy group, X is Cl, n=2, m=0.

3. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The enol is selected from the monomers shown in formula (G1). Formula (G1) L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

4. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The unsaturated carboxylic acid is selected from the monomers shown in formula (G2). Formula (G2) L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, and L4 is selected from C1-C30 alkylene groups with side groups.

5. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The unsaturated carboxylic acid ester is selected from the monomers shown in formula (G3). Formula (G3) Among them, L2, L3, and L5 are each independently selected from H or C1-C30 alkyl groups, L4 is selected from C1-C30 alkylene groups with side groups, and L6 is selected from C1-C30 alkyl groups.

6. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The additive is selected from one or more of organoaluminum compounds, organoboron compounds, and organosilicon compounds.

7. The coordination precipitation polymerization method for olefin polymerization according to claim 6, characterized in that, The organoaluminum compound is AlY. n X 1 3-n Wherein, Y is selected from H, C1-C20 saturated or unsaturated hydrocarbon groups, and C1-C20 saturated or unsaturated hydrocarbon oxygen groups; X 1 Selected from halogens; 0 <n≤3。 8. The coordination precipitation polymerization method for olefin polymerization according to claim 7, characterized in that, Y is selected from C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl, or C6-C20 aryl; X 1 Selected from chlorine or bromine.

9. The coordination precipitation polymerization method for olefin polymerization according to claim 6, characterized in that, The organoboron compound is an aromatic boron and / or a borate.

10. The coordination precipitation polymerization method for olefin polymerization according to claim 9, characterized in that, The aromatic boron is selected from substituted or unsubstituted phenyl boron.

11. The coordination precipitation polymerization method for olefin polymerization according to claim 10, characterized in that, The aromatic boron group is tris(pentafluorophenyl)boron.

12. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6-11, characterized in that, The borate is selected from N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate and / or triphenylmethyl tetra(pentafluorophenyl)borate.

13. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6-11, characterized in that, The organosilicon compound is an alkylsilane compound.

14. The coordination precipitation polymerization method for olefin polymerization according to claim 13, characterized in that, The general formula of the alkylsilicon compound is SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl groups, and H2, H3 and H4 are each independently selected from C1-C10 alkyl groups or halogens.

15. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6-8, characterized in that, When the additive contains an organoaluminum compound, the molar ratio of the amount of aluminum in the organoaluminum compound to the amount of M in the catalyst is (10-10000000):

1.

16. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6 and 9-11, characterized in that, When the auxiliary contains an organoboron compound, the molar ratio of the amount of boron in the organoboron compound to the amount of M in the catalyst is (0.1-1000):

1.

17. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6 and 13-14, characterized in that, When the additive contains an organosilicon compound, the molar ratio of the amount of silicon in the organosilicon compound to the amount of M in the catalyst is (10-10000000):

1.

18. The coordination precipitation polymerization method for olefin polymerization according to any one of claims 6-11 and 14, characterized in that, When the additive is a combination of organoaluminum compound, organoboron compound and organosilicon compound, the molar ratio of the total amount of aluminum, boron and silicon in the additive to the amount of M in the catalyst is (10-11000000):

1.

19. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The polymerization reaction is carried out in the presence of a solvent.

20. The coordination precipitation polymerization method for olefin polymerization according to claim 19, characterized in that, The solvent is selected from one or more of alkanes, haloalkanes, and aromatic hydrocarbons.

21. The coordination precipitation polymerization method for olefin polymerization according to claim 20, characterized in that, The alkane is selected from one or more of C3-C20 alkanes.

22. The coordination precipitation polymerization method for olefin polymerization according to claim 20, characterized in that, The general formula of the haloalkanes is R 1 X 2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogens, m2+n2≥1, R 1 Selected from C1-C10 alkyl or alkenyl groups, R 2 Selected from C1-C10 alkylene or alkenylene groups.

23. The coordination precipitation polymerization method for olefin polymerization according to claim 20, characterized in that, The general formula of the aromatic hydrocarbon is R 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl, and C1-C10 alkanes.

24. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that, The polymerization reaction conditions include: a temperature of -50 to 180°C and a time of 10 to 200 minutes.

25. The polyolefin prepared by the coordination precipitation polymerization method for olefin polymerization according to any one of claims 1-24, characterized in that, The polyolefin is spherical or near-spherical in shape.

26. The polyolefin according to claim 25, characterized in that, The average particle size of the polyolefin is 0.02-50 mm.

27. The polyolefin according to claim 25 or 26, characterized in that, The weight-average molecular weight of the polyolefin is 10,000-800,000.

28. The polyolefin according to claim 25 or 26, characterized in that, The molecular weight distribution index of the polyolefin is ≤10.

29. The polyolefin according to claim 25 or 26, characterized in that, The melting point of the polyolefin is 90-140℃.

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